THE SYNTHESIS OF 1-PHENYLAZO-2-NAPHTHOL

ABSTRACT

I. INTRODUCTION

Azo-compounds,
compounds
with
general formula
patterns are
coupling products from the reaction of
arenediazonium salts
with phenols
and other amines. Azo dyes are easily prepared
using the coupling mechanism resulting to its
cheap large-scale manufacturing cost. Azo
compounds are brightly colored compounds due
to optical reactivity with light of it chromopore
functional group,
. Sudan-1 of 1phenylazo-2-naphthol is synthesized in this
experiment.
Dyeing the textile using azo-dyes
requires different techniques in accordance to
the nature of the textile fabric to be processed. A
textile which cannot be dyed using simple
adsorption undergoes ingrain dyeing wherein the
azo dye is made right in the middle of microspaces between the fabrics.
The general reaction pattern for Sudan
synthesis first undergoes azotization and then
coupling reaction with highly activated aromatic
compounds.

II. METHODOLOGY

Figure 1. The general reaction pattern for the

azotization-coupling reaction includes two-step
process.
The physical properties of the obtained
crystal such as melting point and boiling point
are then determined to provide comparison with
commercially produced Sudan dyes.

III. RESULTS AND DISCUSSION

Aniline is reacted with NaNO2 crystals
under extremely acidic solutions using HCl or
H2SO4 in a very cold temperature. The
phenyldiazonium
intermediate
easily
decomposes back into its aniline counterpart at
slightly higher temperature, thus the solution is
maintained in an ice bath a constant temperature
of 5OC. The reaction for diazotization process is:

Figure 2. The formation of azonium salt is

achieved by the azotization reaction at 0OC.
The diazonium salt by-product is very
reactive. It can be used to yield different kinds
of substituted benzene products like aryl halides,
aryl amide and phenols. Alkyl amine can also be
synthesized by reacting it with NaNO2 or HNO2
to yield alkanediazonium product; however, the
reaction by product cannot be isolated due to its
high reactivity.
The azotization process starts with the
bimolecular exchange of proton and N, in which
the nitrogen lone pairs create triple bonds with
the N from NaNO2.

Figure 3. The mechanism of formation of

azonium ion by the bimolecular attack of nitrite
to the aniline.
The phenyldiazonium salt byproduct
then undergoes either nucleophilic substitution
of diazonium-coupling reaction. In diazoniumcoupling reaction the diazonium salt attacks the
carbon in the para- and ortho- position with
respect to the activating substituent of the
benzene. For this experiment -naphthol couples
with the diazonium salt forming a resonancestabilized intermediate.

Figure 4. The coupling reaction of the

diazonium salt with -naphthol occurs with the
attack of the diazonium salt with on the paracarbon of the -naphthol.
The attack of the diazonium salt the
carbon next to the OH in the -naphthol is
favored due to the presence of more resonance
representation for the products.

Figure 6. Side reaction due to the nucleophilic

substitution of a nucleophile such as OH or
NR2 with the azo-group in th ediazonium salt.
The decomposition of diazonium salt
also occurs if the solution is not kept at the
advised temperature. The diazonium salt easily
reverses back to aniline a slightly higher
temperature than the boiling point. The overall
result is the low percent yield for the azo
compounds.

Figure 5. Some of the resonance structure of the

coupling reaction intermediate.
The final coupling product is Sudan-1
or 1-phenylazo-2-naphthol azo dye.
Rock salt is added in the ice bath
because in induces the colligative property of
solution called freezing point lowering. Thus, ice
melts at a much lower temperature below OOC.
Among the possible side reaction in the
experiment is the direct substitution of any
nucleophile present in the interacting solution.
In this case the diazonium salt in the reaction
can be made into a phenol by the direct
substitution of OH in the solution. Other
nucleophiles such as NR2 or NH2 can also
easily substitute the azo-group in the
intermediate salt.

A good dye is the one that bonds

perfectly well with clothes fiber. The presence
of functional group responsible for the
intermolecular attraction of the dye molecules
and the fiber ensures adhesion of the dye to the
textile. An ideal dye should then contain groups
that bonds with most types of fabrics. Sudan-1
contains molecules incapable of direct bonding
with the cotton fiber. The adhesion between the
Sudan molecules and the cotton fiber is very
weak. In cases like this, ingrain dyeing is the
most appropriate for this application. In the
process of ingrain dyeing, the Sudan dye is
synthesized right in the spaces between the
fibers such that they are permanently trapped
inside the fiber spaces of the cotton.
Application
Diazotization products are powerful
reaction intermediate that can be used to
synthesize many monosubstituted aromatic
compounds.
The following amine pair and aryl
compounds are used to synthesize the final
product shown on the right.
Synthesis of butter yellow a (artificial
colors of butters) can also be produced using the
usual azotization and coupling reaction. Butter
yellow is primarily used nowadays to study
carcinogenesis and other medicine related
chemical reactions.
Recommendation

IV. REFERENCES

Alsoph, C. et al. Elements of Organic Chemistry

as Revealed by the Scientific Method.
Massachusetts: Addison-Wesley Publishing
Company. 1996
Brown, W. H. et al. Introduction to Organic
Chemistry 3rd edition. New Jersey: John Wiley
and Sons, Inc. 2005.
McMurry, J. Organic Chemistry 6th edition. New
York: Brookes/Cole-Thomson. 2004.
Organic Chemistry Laboratory Manual.
Institute of Chemistry, University of the
Philippines Diliman. 2006.
Young, H. et al. University Physics.
Massachusetts: Addison-Wesley Publishing
Company. 2004.